Formation and occurrence of dimer esters of pinene oxidation products in atmospheric aerosols

K. Kristensen; Kirsten Enggrob; Stephanie Michelle King; D. R. Worton; S.M. Platt; R. Mortensen; Thomas Rosenoern; J. D. Surratt; Merete Bilde; A. H. Goldstein; Marianne Glasius

doi:10.5194/acp-13-3763-2013

Formation and occurrence of dimer esters of pinene oxidation products in atmospheric aerosols

K. Kristensen, Kirsten Enggrob, Stephanie Michelle King, D. R. Worton, S.M. Platt, R. Mortensen, Thomas Rosenoern, J. D. Surratt, Merete Bilde, A. H. Goldstein, Marianne Glasius

Department of Chemistry

Abstract

The formation of carboxylic acids and dimer esters from alpha-pinene oxidation was investigated in a smog chamber and in ambient aerosol samples collected during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX). Chamber experiments of alpha-pinene ozonolysis in dry air and at low NOx concentrations demonstrated formation of two dimer esters, pinyl-diaterpenyl (MW 358) and pinonyl-pinyl dimer ester (MW 368), under both low- and high-temperature conditions. Concentration levels of the pinyl-diaterpenyl dimer ester were lower than the assumed first-generation oxidation products cis-pinic and terpenylic acids, but similar to the second-generation oxidation products 3-methyl-1,2,3-butane tricarboxylic acid (MBTCA) and diaterpenylic acid acetate (DTAA). Dimer esters were observed within the first 30 min, indicating rapid production simultaneous to their structural precursors. However, the sampling time resolution precluded conclusive evidence regarding formation from gas- or particle-phase processes. CCN activities of the particles formed in the smog chamber displayed a modest variation during the course of experiments, with kappa values in the range 0.06-0.09 (derived at a supersaturation of 0.19. The pinyl-diaterpenyl dimer ester was also observed in ambient aerosol samples collected above a ponderosa pine forest in the Sierra Nevada Mountains of California during two seasonally distinct field campaigns in September 2007 and July 2009. The pinonyl-pinyl ester was observed for the first time in ambient air during the 2009 campaign, and although present at much lower concentrations, it was correlated with the abundance of the pinyl-diaterpenyl ester, suggesting similarities in their formation. The maximum concentration of the pinyl-diaterpenyl ester was almost 10 times higher during the warmer 2009 campaign relative to 2007, while the concentration of cis-pinic acid was approximately the same during both periods, and lack of correlation with levels of cis-pinic and terpenylic acids for both campaigns indicate that the formation of the pinyl-diaterpenyl ester was not controlled by their ambient abundance. In 2009 the concentration of the pinyl-diaterpenyl ester was well correlated with the concentration of DTAA, a supposed precursor of diaterpenylic acid, suggesting that the formation of pinyl-diaterpenyl dimer was closely related to DTAA. Generally, the pinyl-diaterpenyl ester was found at higher concentrations under higher temperature conditions, both in the smog-chamber study and in ambient air aerosol samples, and exhibited much higher concentrations at night relative to day-time in line with previous results. We conclude that analysis of pinyl dimer esters provides valuable information on pinene oxidation processes and should be included in studies of formation and photochemical aging of biogenic secondary organic aerosols, especially at high temperatures.

Original language	English
Journal	Atmospheric Chemistry and Physics
Volume	13
Issue number	7
Pages (from-to)	3763-3776
Number of pages	14
ISSN	1680-7316
DOIs	https://doi.org/10.5194/acp-13-3763-2013
Publication status	Published - 2013

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@article{e0b16a8e80874c4cb660ad474c4d8e41,

title = "Formation and occurrence of dimer esters of pinene oxidation products in atmospheric aerosols",

abstract = "The formation of carboxylic acids and dimer esters from alpha-pinene oxidation was investigated in a smog chamber and in ambient aerosol samples collected during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX). Chamber experiments of alpha-pinene ozonolysis in dry air and at low NOx concentrations demonstrated formation of two dimer esters, pinyl-diaterpenyl (MW 358) and pinonyl-pinyl dimer ester (MW 368), under both low- and high-temperature conditions. Concentration levels of the pinyl-diaterpenyl dimer ester were lower than the assumed first-generation oxidation products cis-pinic and terpenylic acids, but similar to the second-generation oxidation products 3-methyl-1,2,3-butane tricarboxylic acid (MBTCA) and diaterpenylic acid acetate (DTAA). Dimer esters were observed within the first 30 min, indicating rapid production simultaneous to their structural precursors. However, the sampling time resolution precluded conclusive evidence regarding formation from gas- or particle-phase processes. CCN activities of the particles formed in the smog chamber displayed a modest variation during the course of experiments, with kappa values in the range 0.06-0.09 (derived at a supersaturation of 0.19. The pinyl-diaterpenyl dimer ester was also observed in ambient aerosol samples collected above a ponderosa pine forest in the Sierra Nevada Mountains of California during two seasonally distinct field campaigns in September 2007 and July 2009. The pinonyl-pinyl ester was observed for the first time in ambient air during the 2009 campaign, and although present at much lower concentrations, it was correlated with the abundance of the pinyl-diaterpenyl ester, suggesting similarities in their formation. The maximum concentration of the pinyl-diaterpenyl ester was almost 10 times higher during the warmer 2009 campaign relative to 2007, while the concentration of cis-pinic acid was approximately the same during both periods, and lack of correlation with levels of cis-pinic and terpenylic acids for both campaigns indicate that the formation of the pinyl-diaterpenyl ester was not controlled by their ambient abundance. In 2009 the concentration of the pinyl-diaterpenyl ester was well correlated with the concentration of DTAA, a supposed precursor of diaterpenylic acid, suggesting that the formation of pinyl-diaterpenyl dimer was closely related to DTAA. Generally, the pinyl-diaterpenyl ester was found at higher concentrations under higher temperature conditions, both in the smog-chamber study and in ambient air aerosol samples, and exhibited much higher concentrations at night relative to day-time in line with previous results. We conclude that analysis of pinyl dimer esters provides valuable information on pinene oxidation processes and should be included in studies of formation and photochemical aging of biogenic secondary organic aerosols, especially at high temperatures.",

author = "K. Kristensen and Kirsten Enggrob and King, {Stephanie Michelle} and Worton, {D. R.} and S.M. Platt and R. Mortensen and Thomas Rosenoern and Surratt, {J. D.} and Merete Bilde and Goldstein, {A. H.} and Marianne Glasius",

year = "2013",

doi = "10.5194/acp-13-3763-2013",

language = "English",

volume = "13",

pages = "3763--3776",

journal = "Atmospheric Chemistry and Physics",

issn = "1680-7316",

publisher = "Copernicus GmbH",

number = "7",

}

TY - JOUR

T1 - Formation and occurrence of dimer esters of pinene oxidation products in atmospheric aerosols

AU - Kristensen, K.

AU - Enggrob, Kirsten

AU - King, Stephanie Michelle

AU - Worton, D. R.

AU - Platt, S.M.

AU - Mortensen, R.

AU - Rosenoern, Thomas

AU - Surratt, J. D.

AU - Bilde, Merete

AU - Goldstein, A. H.

AU - Glasius, Marianne

PY - 2013

Y1 - 2013

N2 - The formation of carboxylic acids and dimer esters from alpha-pinene oxidation was investigated in a smog chamber and in ambient aerosol samples collected during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX). Chamber experiments of alpha-pinene ozonolysis in dry air and at low NOx concentrations demonstrated formation of two dimer esters, pinyl-diaterpenyl (MW 358) and pinonyl-pinyl dimer ester (MW 368), under both low- and high-temperature conditions. Concentration levels of the pinyl-diaterpenyl dimer ester were lower than the assumed first-generation oxidation products cis-pinic and terpenylic acids, but similar to the second-generation oxidation products 3-methyl-1,2,3-butane tricarboxylic acid (MBTCA) and diaterpenylic acid acetate (DTAA). Dimer esters were observed within the first 30 min, indicating rapid production simultaneous to their structural precursors. However, the sampling time resolution precluded conclusive evidence regarding formation from gas- or particle-phase processes. CCN activities of the particles formed in the smog chamber displayed a modest variation during the course of experiments, with kappa values in the range 0.06-0.09 (derived at a supersaturation of 0.19. The pinyl-diaterpenyl dimer ester was also observed in ambient aerosol samples collected above a ponderosa pine forest in the Sierra Nevada Mountains of California during two seasonally distinct field campaigns in September 2007 and July 2009. The pinonyl-pinyl ester was observed for the first time in ambient air during the 2009 campaign, and although present at much lower concentrations, it was correlated with the abundance of the pinyl-diaterpenyl ester, suggesting similarities in their formation. The maximum concentration of the pinyl-diaterpenyl ester was almost 10 times higher during the warmer 2009 campaign relative to 2007, while the concentration of cis-pinic acid was approximately the same during both periods, and lack of correlation with levels of cis-pinic and terpenylic acids for both campaigns indicate that the formation of the pinyl-diaterpenyl ester was not controlled by their ambient abundance. In 2009 the concentration of the pinyl-diaterpenyl ester was well correlated with the concentration of DTAA, a supposed precursor of diaterpenylic acid, suggesting that the formation of pinyl-diaterpenyl dimer was closely related to DTAA. Generally, the pinyl-diaterpenyl ester was found at higher concentrations under higher temperature conditions, both in the smog-chamber study and in ambient air aerosol samples, and exhibited much higher concentrations at night relative to day-time in line with previous results. We conclude that analysis of pinyl dimer esters provides valuable information on pinene oxidation processes and should be included in studies of formation and photochemical aging of biogenic secondary organic aerosols, especially at high temperatures.

AB - The formation of carboxylic acids and dimer esters from alpha-pinene oxidation was investigated in a smog chamber and in ambient aerosol samples collected during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX). Chamber experiments of alpha-pinene ozonolysis in dry air and at low NOx concentrations demonstrated formation of two dimer esters, pinyl-diaterpenyl (MW 358) and pinonyl-pinyl dimer ester (MW 368), under both low- and high-temperature conditions. Concentration levels of the pinyl-diaterpenyl dimer ester were lower than the assumed first-generation oxidation products cis-pinic and terpenylic acids, but similar to the second-generation oxidation products 3-methyl-1,2,3-butane tricarboxylic acid (MBTCA) and diaterpenylic acid acetate (DTAA). Dimer esters were observed within the first 30 min, indicating rapid production simultaneous to their structural precursors. However, the sampling time resolution precluded conclusive evidence regarding formation from gas- or particle-phase processes. CCN activities of the particles formed in the smog chamber displayed a modest variation during the course of experiments, with kappa values in the range 0.06-0.09 (derived at a supersaturation of 0.19. The pinyl-diaterpenyl dimer ester was also observed in ambient aerosol samples collected above a ponderosa pine forest in the Sierra Nevada Mountains of California during two seasonally distinct field campaigns in September 2007 and July 2009. The pinonyl-pinyl ester was observed for the first time in ambient air during the 2009 campaign, and although present at much lower concentrations, it was correlated with the abundance of the pinyl-diaterpenyl ester, suggesting similarities in their formation. The maximum concentration of the pinyl-diaterpenyl ester was almost 10 times higher during the warmer 2009 campaign relative to 2007, while the concentration of cis-pinic acid was approximately the same during both periods, and lack of correlation with levels of cis-pinic and terpenylic acids for both campaigns indicate that the formation of the pinyl-diaterpenyl ester was not controlled by their ambient abundance. In 2009 the concentration of the pinyl-diaterpenyl ester was well correlated with the concentration of DTAA, a supposed precursor of diaterpenylic acid, suggesting that the formation of pinyl-diaterpenyl dimer was closely related to DTAA. Generally, the pinyl-diaterpenyl ester was found at higher concentrations under higher temperature conditions, both in the smog-chamber study and in ambient air aerosol samples, and exhibited much higher concentrations at night relative to day-time in line with previous results. We conclude that analysis of pinyl dimer esters provides valuable information on pinene oxidation processes and should be included in studies of formation and photochemical aging of biogenic secondary organic aerosols, especially at high temperatures.

U2 - 10.5194/acp-13-3763-2013

DO - 10.5194/acp-13-3763-2013

M3 - Journal article

SN - 1680-7316

VL - 13

SP - 3763

EP - 3776

JO - Atmospheric Chemistry and Physics

JF - Atmospheric Chemistry and Physics

IS - 7

ER -